Diphenylphosphidoboratabenzene: An anionic analoge of triphenylphosphine
Diphenylphosphidoboratabenzene: An anionic analoge of triphenylphosphine
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DOI：
10.1021/ja9615740
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发表时间：
1996-08-28
影响因子：
15
通讯作者：
Fu, GC
中科院分区：
文献类型：
--
作者：
Hoic, DA;Davis, WM;Fu, GC
受其与无处不在的三苯基膦配体（1）的关系的刺激，我们已经确定了2，并开始探索二苯基磷硼杂苯阴离子（DPB; 2）的配位化学。DPB可以被看作是一个带负电荷的，基本上是电子等排的，PPh 3的变体;在这种情况下，PPh 3和DPB配合物的比较研究，无论是对于一个给定的金属和元素周期表中相邻的金属，可能会导致有用的新的见解反应性。本文报道了DPB的化学研究的第一阶段，具体地说，合成和结构工作确立了DPB作为一系列过渡金属配体的可行性。通过与二苯基磷硼杂苯钾（K-DPB）处理过渡金属卤化物，可以生成各种DPB加合物。例如，Cp 2 ZrHCl与K-DPB在PMe 3存在下的反应导致氯化物配体的置换并形成Cp 2 ZrH-（DPB）（PMe 3）（3;当量1）。该配合物的单晶X射线衍射研究（图1a;表1a）4显示了与Cp 2 ZrH（SiPh 3）（PMe 3）非常相似的结构。5 DPB配体的PC键比PB键短约0.12 π，配体采用轻微扭曲的四面体构型。
Stimulated by its relationship to the ubiquitous triphenylphosphine ligand (1), 1 we have prepared2 and begun to explore the coordination chemistry of the diphenylphosphidoboratabenzene anion (DPB; 2). DPB may be viewed as a negatively charged, essentially isosteric, variant of PPh3; within this context, comparative studies of PPh3 and DPB complexes, both for a given metal and for metals which are adjacent in the periodic table, could lead to useful new insights into reactivity. 3 In this communication, we report the first stage of our investigation into the chemistry of DPB, specifically, synthetic and structural work which establishes the viability of DPB as a ligand for an array of transition metals.A wide range of DPB adducts can be generated through treatment of transition metal halides with potassium diphenylphosphidoboratabenzene (K-DPB). For example, reaction of Cp2ZrHCl with K-DPB in the presence of PMe3 leads to displacement of the chloride ligand and formation of Cp2ZrH-(DPB)(PMe3)(3; eq 1). A single-crystal X-ray diffraction study of this complex (Figure 1a; Table 1a) 4 reveals a structure very similar to that found for Cp2ZrH (SiPh3)(PMe3). 5 The PC bonds of the DPB ligand are∼ 0.12 Å shorter than the PB bond, and the ligand adopts a slightly distorted tetrahedral geometry.